WO2003053536A1 - Nouveaux desemulsionneurs, leur preparation et leur utilisation dans des formations petroliferes - Google Patents

Nouveaux desemulsionneurs, leur preparation et leur utilisation dans des formations petroliferes Download PDF

Info

Publication number
WO2003053536A1
WO2003053536A1 PCT/US2002/039869 US0239869W WO03053536A1 WO 2003053536 A1 WO2003053536 A1 WO 2003053536A1 US 0239869 W US0239869 W US 0239869W WO 03053536 A1 WO03053536 A1 WO 03053536A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
amine
polymeric composition
composition according
grams
Prior art date
Application number
PCT/US2002/039869
Other languages
English (en)
Inventor
Duane S. Treybig
Dennis A. Williams
K. T. Chang
Original Assignee
Ondeo Nalco Energy Services, L.P.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ondeo Nalco Energy Services, L.P. filed Critical Ondeo Nalco Energy Services, L.P.
Priority to AU2002360587A priority Critical patent/AU2002360587A1/en
Publication of WO2003053536A1 publication Critical patent/WO2003053536A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/045—Breaking emulsions with coalescers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to new demulsification compounds and formulations.
  • this invention relates to the demulsification of oil-bearing formations that have been treated with novel N-alkylated polyhydroxyetheramines.
  • Acid or other chemical based extraction of oil-bearing deposits can lead to emulsion formation within the extracted phase from the deposit. These emulsions can make it extremely difficult to remove the oil content from the deposit.
  • "Demulsifiers” are used as one chemical means of destroying or “breaking” such unwanted emulsions. This process is defined in Hawley's 11 th Chemical Dictionary, Van Nostrand Reinold Company Inc., N. Irving Sax, ed., (p.352), 1987, as "Demulsification”.
  • Chemical means of breaking an emulsion include the addition of polyvalent ion sources or a material such as nonylphenol, to the emulsion. However, while such materials provide some measure of utility in demulsification, there is still an ongoing need for more effective and useful demulsifiers.
  • the present invention is directed to novel oligo- and polymeric compounds, compositions and their methods of preparation and use.
  • These materials primarily aliphatic polyhydroxyetheramines and quarternized aliphatic polyhydroxyetheramines, are broadly useful in demulsifing (emulsified) hydrocarbons and more specifically, demulsifing oil-bearing formations that have been extracted/digested with, for example, organic or inorganic acids. It has been discovered that these new oligo- or polymeric demulsifiers can be obtained by reacting amines or amine containing groups having two reactive amino hydrogens with aliphatic diglycidyl ethers of diols, and/ or epoxidized olefins.
  • Additional demulsifiers according to the invention can be obtained using a second amine-containing group wherein the second amine-containing group incorporates a tertiary amine group. Additional demulsifiers according to the invention can be obtained by "capping" some or all of the remaining epoxy groups on the basic polyhydroxyetheramine with various additional amine-containing groups.
  • the amino- or amine groups of the oligomeric and polymeric demulsifiers can be alkylated or quatemized with an N-alkylating agent containing-group such as epihalohydrin-containing groups to provide novel demulsifiers.
  • a first embodiment of a new polymeric demulsifier obtained by reacting an amine or amine-containing group having two reactive amino hydrogens with an aliphatic diglycidyl ether of a diol, or an epoxidized olefin, or mixtures thereof.
  • a second embodiment obtained by reacting a first amine or amine-containing group having two reactive amino hydrogens and a second amine or amine-containing group having two reactive amino hydrogens and a tertiary amine group with an aliphatic diglycidyl ether of a diol, or an epoxidized olefin or mixtures thereof.
  • a third embodiment obtained by reacting an amine or amine-containing group having two reactive amino hydrogens with an aliphatic diglycidyl ether of a diol or an epoxidized olefin, or mixtures thereof and subsequently "capping" (i. e. reacting some or all of) the unreacted epoxy groups with an amine or amine-containing group having one or two reactive amino hydrogens.
  • a forth embodiment is obtained by reacting a mixture of an amine or amine- containing group having two reactive amino hydrogens, and an amine or polyamine having two reactive amino hydrogens and a tertiary amine group, with an aliphatic diglycidyl ether of a diol or an epoxidized olefin or a mixture of these and subsequently "capping" some or all of the remaining epoxy groups on the resulting compound with an amine or amine- containing group having one or two reactive amino hydrogens.
  • the capping amine can further comprise tertiary amine groups.
  • a fifth embodiment is obtained by grafting an N-alkylating agent-containing group, such as epihalohydrin-capped polyalkylene glycol methyl ether, onto any of embodiments 1, 2, 3 or 4 to thereby produce novel compounds useful in demulsifing an emulsified hydrocarbon such as an oil-bearing formation.
  • an N-alkylating agent-containing group such as epihalohydrin-capped polyalkylene glycol methyl ether
  • a sixth embodiment of the present invention is obtained by formulating any one of the previously disclosed demulsifier compounds with suitable solvents, such as alcohols, various alkyl or substituted alkoxy copolymers; phenol-formaldehyde resins (e.g. resoles and novalacs, or other resins or similar compounds known in the art).
  • suitable solvents such as alcohols, various alkyl or substituted alkoxy copolymers; phenol-formaldehyde resins (e.g. resoles and novalacs, or other resins or similar compounds known in the art).
  • the formulation can further comprise organic or inorganic acids, or mixtures of acids, to obtain a demulsifier formulation which is easily and conveniently used to treat an emulsified oil bearing formation to break or preclude emulsion formation.
  • a seventh embodiment of the present invention provides processes for the treatment of oil bearing formations to break emulsions resulting from acid or other ionic or nonionic stimulation of an oil or hydrocarbon formation.
  • An, eighth embodiment of the present invention provides methods and processes for the production of the novel demulsifier compounds and compositions.
  • Suitable amines and amine-containing group compounds or monomers useful in the various embodiments of the invention are those amines having only two reactive amino hydrogens and may be represented by but are not limited to the following formulas:
  • Zl Zl R is a C 2 -C 10 alkyl group; either a saturated, unsaturated, or substituted alkyl, with ethylene and propylene being the most preferred groups. Also useful in the present invention are hydroxy or hydroxy- alkyl substituted C 2 -C ⁇ 0 saturated or unsaturated hydrocarbons; Rl can be an alkoxy radical which can be represented by the formula:
  • R2 is a C 2 -C 10 alkylene radical or substituted C 2 -C 10 alkylene radical wherein the carbons can be further substituted with various groups, including alkylamido, hydroxy, alkoxy, halogen, cyano, dialkylamino, aryloxy-, alkylcarbonyl(e.g. ketonic group) or arylcarbonyl groups.
  • Ethylene is the most preferred R2 substituted;
  • R3 is a C 2 -C 20 alkylene (alkyl radical or hydrocarbyl group; saturated or unsaturated), or R3 in certain preferred embodiments is phenyl, ethylene and hexane.
  • R3 can also be a substituted C 2 -C 20 alkylene wherein the carbon atoms can be further substituted with various groups including: alkylamido, hydroxy, alkoxy, halo, cyano, aryloxy, alkylcarbonyl, arylcarbonyl, alkylamido, and dialkylamine. Hydroxy- and alkoxy- groups are the more preferred substituents on the R3 radical.
  • Z can be hydrogen, alkylamido, hydroxy, dialkylamine, alkoxy, halogen, aryloxy, cyano, alkylcarbonyl, or arylcarbonyl, or a nitrogen containing moiety such as piperidine, morpholine, pyrrolidine, pyridine or other heterocyclic- aliphatic or heterocyclic-aromatic compound.
  • Preferred Z substituents include alkylamido, hydroxy, dialkylamino and alkoxy groups.
  • a preferred dialkylamine is dimethylamine and a preferred Zl is hydrogen, an alkyl or an acyl group with hydrogen and methyl most preferred.
  • Suitable amines represented by formula (1) include, but are not limited to methylamine, ethylamine, propylamine, butylamine, sec-butylamine, isobutylamine, 3,3- dimethylbutylamine, hexylamine, benzylamine, 2-amino-l-butanol, 4-amino-l-butanol, 2- amino-2-methyl-l-propanol, 6-amino-l-hexanol, ethanolamine, propanolamine, tris(hydroxymethyl)aminomethane,
  • Suitable amines represented by formula (2) include but are not limited to polyoxyalkylenamines, such as the Jeffamine M-seriesTM available from Huntsman Chemical Corporation, USA.
  • the Jeffamine M-series of compounds are made by the reaction of a monohydric alcohol initiator with ethylene and/or propylene oxide(s), followed by conversion of the resulting terminal hydroxyl group to an amine group.
  • the preferred M-seriesTM amines have the general structure in formula (7):
  • R4 is an alcohol initiator and is usually CH 3 O-
  • R5 is either hydrogen or -CH 3 and n is in the range of 1 to about 45.
  • Suitable amines represented by formula (3) include but are not limited to ethoxylated and propoxylated ethyleneamines such as 2-(2-aminoethylamino)ethanol.
  • n may vary from 0 to 20.
  • Suitable amines represented by formula (4) include, but are not limited to piperazine, 2-methyl piperazine, 2,6-dimethylpiperazine and 2-(methylamido)piperazine.
  • Suitable amines represented by formula (5) include, but are not limited to N,N'- bis(2-hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, N,N'-dimethyl-l ,4- phenylenediamine and N,N'dimethyl-l,6-hexanediamine. It has been surprisingly discovered that the presence of tertiary amine group substituents on the backbone polymer can enhance the grafting of an N-alkylating agent group-containing compound to form the novel demulsifiers of the present invention. Such tertiary amine groups are preferred in demulsifiers of the invention.
  • Examples of amines having two reactive amino groups and substituted with a tertiary amine group are 3- (dimethylamino)propylamine; N,N-dimethyl ethyl enediamine; N,N- di ethyl ethylenediamine; l-(2-aminoethyl)piperidine; 4-(2-aminoethyl)morpholine; 2-(2- aminoethyl)-l-methylpyrrolidine; l-(2-aminoethyl)pyrrolidine; and 2-(2- aminoethyl)pyridine.
  • Extended tertiary amines for reaction with an N-alkylating agent can also be provided by ditertiary amine end groups.
  • the quantity of an amine having two reactive amino hydrogens and a tertiary amine group can comprise 0 to 50 mole % of the total amines having two reactive amino hydrogens reacted with the diepoxide or diglycidyl-containing group compound, depending on which amine having two reactive amino hydrogens and a tertiary amine group is reacted.
  • 3-(dimethylamino) propylamine comprises 0 to about 10 %, preferably 0 to 6% and most preferably 0 to 2 mole % of the total amines having two reactive amino hydrogens in a preferred embodiment.
  • Other suitable amines will be known to those of ordinary skill in the art.
  • the Epoxide and Glycidyl Compounds The amine can be reacted with an aliphatic or cycloaliphatic compound having two reactive epoxide groups, e.g. a diepoxy-compound such as a diglycidyl ether of a diol, or an epoxidized olefin to produce embodiments of the present invention.
  • a diepoxy-compound such as a diglycidyl ether of a diol
  • the diglycidyl ether of a diol is represented by the following structure in formula (8):
  • R6 is a C 2 to C 20 alkyl radical, alkyl substituted C 2 to C 20 alkyl radical, C 2 to C 40 alkoxy, or a C 2 to C 40 hydroxy-substituted alkoxy- group radical; n can vary from 0 to about 20, and is preferably in the range of 0 to about 10.
  • Suitable diglycidyl ethers of diols according to formula (8) include, but are not limited to: bis(2,3-epoxypropyl)ether, diglycidyl ether of 1 ,4-butanediol, diglycidyl ether of neopentyl glycols, diglycidyl ether of ethylene glycols, glycerol diglycidyl ethers, diglycidyl ether of polyethyleneglycols, diglycidyl ethers of polypropylene glycols, diglycidyl ethers of glycols from the reaction product of ethylene oxide and propylene oxide thereby producing poly( ethoxy-propyloxy) polymer, including block copolymers.
  • diglycidyl ethers of diols not represented by the above formula include diglycidyl ethers of cyclohexane dimethanol and diglycidyl esters of organic dimer acids, for example, 1,4-cyclohexandimethanol diglycidyl ether.
  • the epoxidized olefins can be represented by the structure in formula (9):
  • R7 is a C 2 to C 20 alkyl radical or an alkyl substituted C 2 to C 20 alkylene group moiety.
  • Suitable epoxidized olefins include 1,2,3,4-diepoxybutane; 1,2,7,8-diepoxyoctane and 1,2,9, 10-diepoxydecane. Cyclodiepoxidized olefins including 1,2,5,6- diepoxycyclooctane are also useful in certain embodiments of the invention. The most preferred epoxidized olefin is 1,2,7,8-diepoxyoctane.
  • Triepoxides can be mixed with diepoxides to provide branching and crosslinking points to provide additional embodiments of the inventive demulsifier.
  • Suitable aliphatic triepoxides include, but are not limited to trimethyol propane triglycidyl ether, the polyglycidyl ethers of castor oil, polyglycidyl ethers of aliphatic polyols, and aromatic tri epoxy derived compounds such as 1, 3, 5 triglycidyl benzene and the like.
  • the triepoxy- compound can be mixed in amounts effective to provide branching points while not affecting or limiting solubility.
  • the amounts of the triepoxides can be as much as 25 wt.%., preferably less than five wt.% and most preferably less than one weight percent.
  • tetra-functional glycidyl or epoxide -containing compounds can be used as branch points. Such compounds may be derived from various polyols known in the art.
  • the reactants can be mixed at a mole ratio of the amines, having two reactive amino hydrogens, to the diepoxide or diglycidyl-containing compounds of from about 0.8: 1 to about 1.3: 1.
  • a mole ratio of from about 0.9:1 to 1.1: 1 is useful and most preferably a molar ratio of from about 1 : 1 to about 1.05:1 is useful.
  • the reaction of the present invention is very exothermic: a solvent and external cooling to control the exothermic nature of the reaction when prepared in a batch reactor can be used.
  • Suitable solvents are, preferably water, or alcohol soluble solvents such as di(propylene glycol) methyl ether, 2-methoxyethyl ether and the like as would be known to a skilled artisan.
  • the initial reaction is conducted under a blanket of nitrogen or another inert gas.
  • the initial reaction is conducted at a temperature of from about 25 °C to about 240 °C, more preferably at a temperature of about 25 °C to 150 ° C and most preferably at a temperature of 25 to 100 C.
  • subsequent reaction(s) is (are) carried out between about 140 ° and 200 °C, preferably between 140 ° and 180 °C and most preferably between about 140 ° and 160 °C.
  • the reaction can be carried out over a time of from 10 minutes to 100 hours or more, depending on the reactants used and viscosity( i.e. degree of polymerization) desired.
  • the reaction can be conducted neat, in a batch reactor, or in an extruder depending on the desired product.
  • the viscosity of these materials depending on the percent solids (which can range from about 10% to 100%), is in the range of 500 cps to about 2,000,000 cps.
  • Amine end groups are synthesized by "capping" the linear, or branched polymer's terminal epoxide groups.
  • a "capped" polymer is one in which unreacted epoxy groups have been reacted with amine containing groups.
  • Secondary amine end groups are obtained from subsequent "capping" reactions of the remaining un-reacted epoxide groups with at least one of the amines having two available amino hydrogens.
  • Tertiary amine "capped” end groups can be obtained by reacting un-reacted epoxide groups with amines having at least one available amino hydrogen, such as diethanolamine, diisopropanolamine, N-methyl-D-glucamine, N- methylpropylamine, dimethylamine, di ethylamine, dipropylamine, diisopropylamine and the like.
  • Ditertiary amine end groups can be obtained by reacting the epoxide with amines having one available amino hydrogen substituted with a tertiary amine group such as N, N, N'-trirnethyl-l,3-propanediamine, N,N,N' - trimethylethylenediamine, N,N-dimethyl-N'- ethylethylenediamine, N,N,N'-triethylethylenediamine and like compounds.
  • Ditertiary amine end groups also provide extended tertiary amine groups for grafting the N-alkylating agents such as epichlorohydrin terminated polyethyleneglycol (e.g. MPEG)-containing group compounds onto the polymer backbone.
  • N-alkylating agents such as epichlorohydrin terminated polyethyleneglycol (e.g. MPEG)-containing group compounds onto the polymer backbone.
  • the backbone polymer can vary in percent solids from about 20 to 100 wt. %, preferably from 50 to 80 wt. % and most preferably from 60 to 70 wt.%, in a suitable solvent such as an alcohol, ether or water as needed.
  • a suitable solvent such as an alcohol, ether or water as needed.
  • the viscosity of these polymers is deemed an adequate measure of their molecular weights, or degree of reaction, for the purposes of the invention and can range from about 500 cps to 2,000,000 cps or more, depending on the desired properties of the demulsifier.
  • the resulting polyhydroxyetheramine polymers can be further protonated by reacting with a proton source to provide a protonated polyhydroxyetheramine. Common organic or inorganic acids, such as hydrochloric or sulfuric acid, are used to prepare protonated polymers.
  • N-Alkylating Agents Branches are attached to the polymer backbone by grafting N-alkylating agents such as epihalohydrin-reacted polyalkoxides according to formula (10) or (11):
  • R8 is a functional group provided by reaction to terminate the polyalkoxide
  • R9 is hydrogen or Ci to C 6 alkyl group
  • n is from 1 to 120, preferably 100 to 113
  • m is from 2 to 24
  • X is a halogen atom with chloride and bromide being the most preferred.
  • R8 can be a methyl, hydrogen, C ⁇ -C 6 alkyl, C 6 -do aryl, oxy(2-hydroxy-3-chloropropyl), or oxy(2,3- oxopropyl).
  • alkylating agents are R-X type compounds where R is C to C 24 alkyl or benzyl groups and X are halogen, sulfate or sulfonate groups such as tosylate, methane sulfonate, and trifluromethane sulfonate.
  • Other examples include alcohol sulfonates and alpha olefin sulfonates such as C ⁇ 6 -C ⁇ 8 olefin sulfonate, C 14 -C 16 olefin sulfonate and C 12 -C ⁇ 4 olefin sulfonate and the like.
  • Examples of alcohol sulfates include sodium lauryl sulfate; sodium octyl sulfate; sodium decyl sulfate.
  • Examples of R-X compounds where X is a halide include 1-chlorohexane, 1-bromooctane, 1-chlorooctane, 1-chlorohexadecane, 1-chlorooctadecane, 1-bromooctadecane, and 1-bromohexadecane.
  • the preferred N-alkylating agent containing compound is epichlorohydrin capped polyalkylene glycol methyl ether.
  • the polyalkoxide is polyethyene oxide; when R9 is Ci alkyl group the polyalkoxide is polypropylene oxide; when R9 is C 2 alkyl group, polyethylene oxide is polybutylene oxide and the like.
  • the N-alkylating agent can be added to the polymeric composition in amounts as needed to provide the balance of properties required for the demulsifier.
  • N-alkylating agents such as epihalohydrin reacted polyalkoxides are grafted onto tertiary amine groups on the polyhydroxyetheramine polymer between 40 ° to 100 °C, preferably 60 to 95 °C and most preferably at between 85 ° and 90 °C.
  • the pH also influences the rate of the grafting reaction.
  • the reaction can be carried out at a pH between 7.5 and 12.0, preferably between 8.0 and 9.0 and most preferably between 8.3 and 8.8.
  • the N-alkylating agent is grafted onto the polymer using a weight ratio of between 1 : 1 to 8: 1 of polymer to N-alkylating agent.
  • the resulting grafted demulsifier varies in percent solids from 20 wt. % to 60 wt. %, preferably 25 wt. % to 50 wt. % and most preferably 35 wt. % to 50 wt.
  • the polyhydroxyetheramine polymer can be directly reacted with the N-alkylating agent or the polyhydroxyetheramine can be reacted with an acid, such as hydrochloric acid or sulfuric acid and subsequently reacted with the N-alkylating agent.
  • One method of following the rate of the grafting reaction is to monitor the viscosity. A Brookfield viscometer is typically used. When the viscosity of the graft polymer reaches between 200 and 9000 centipoise (cps) preferably 200 to 5000 cps, and most preferably 400 to 5000 cps, the grafting reaction is deemed sufficient and typically stopped.
  • the pH is between about 2.0 to 7.0 and most preferably about 3.5 to 5.0.
  • Sulfuric acid or hydrochloric acid are the preferred acids, although other acids will work.
  • the demulsifier can be formulated by dissolving about 10 to 70 wt.%, preferably about 50 to 60 wt. %, most preferably about 50 wt.% of the polyhydroxyetheramine backbone polymer or grafted backbone polymer (on a 100 wt. % solids basis) in Ci to C 16 , preferably Ci to Cio and more preferably to C 8 alcohols, or ethers or water or other suitable solvents or mixtures of such solvents as required.
  • Wetting improvement agents are also useful in preparing formulations. These materials include oxyalkylated alcohols, phosphate esters, surface tension modifiers, acid and crude interface modifiers such as arylalkylsulfonic acids or polyglycols.
  • breaking speed improving and stabilizing agents such as polyglycols or alkylene oxide block copolymer blends. These include ethoxylated alcohols, alkylphenol /formaldehyde resins, oxyalkylated alkylphenol/ formaldehyde resins, their blends and their blends with any of the other aforementioned agents or additives as will be known to one of skill in the art. These materials can be added to the formulation, as needed, depending on the nature of the oil or hydrocarbon deposit emulsion being broken. Treating an oil bearing formation with the demulsifier compositions of the present invention generally requires 0.05 to 3 gallons (0.05 to 3 wt.
  • Aqueous acids used to stimulate a well/ hydrocarbon formation include hydrochloric acid, hydrofluoric, sulfamic, acetic acid, formic acid, nitric acid, citric acid, ethyl enediaminetetraacetic acid, nitriloacetic acid, mixtures thereof and the like.
  • Demulsifier formulations for water-in-oil emulsions are usually formulated by dissolving up to about 30 wt.% of the backbone polymer or grafted backbone polymer (on a 100 wt.% solids basis) in hydrocarbons like xylene, heavy aromatic naphtha, Ci to C ⁇ 6 alcohols, and the like.
  • Other materials which are useful include, but are not limited to: wetting improvement agents like oxyalkylated alcohols or phosphate esters; surface tension modifiers; breaking speed improving agents such as polyglycols or alkylene oxide block copolymer blends; stabilizing agents such as polyglycols.
  • emulsion breakers such as polyglycols, ethoxylated alcohols, alkylphenol/formaldehyde resins, oxyalkylated alkyl phenol/ formaldehyde resins, their blends and their blends with any of the aforementioned agents or additives can be added.
  • Example 1 Diglycidyl ether of butanediol (202.24 grams, 0.9999 mole, 202.25 g/mole), ethanolamine (61.23 grams, 1.002 mole) and di(propylene glycol) methyl ether (161.60 grams) were weighed into a 1 -liter resin kettle equipped with a thermocouple and heating device, condenser, stirrer and stirrer assembly and nitrogen purge assembly. The reactor contents were a clear water white liquid.
  • the contents were heated to 90 °C where the reactants exothermed to 137 °C.
  • the reactor contents were heated between 140 ° to 161 °C for a period of 1 hour and 44 minutes and then cooled to room temperature.
  • the reactor contents were an orange colored transparent liquid with a Brookfield viscosity of 4627 cps.
  • the polymer was soluble in water and methanol.
  • the infrared spectra showed a broad band at 3400 cm-1 (OH stretch), a medium band at 1641 cm-1 (OH deformation), a medium bend at 1452 cm-1 (aliphatic bending) and a band at 1109 cm-1 (COC and COH stretch).
  • Example 2 Diglycidyl ether of neopentyl glycol (216.39 grams, 1.0005 moles) and di(propylene glycol)methyl ether (170.0 grams) were weighed into a 1 -liter resin kettle equipped with a thermocouple and heating device, condenser, stirrer and stirrer assembly and nitrogen purge assembly. The contents were heated to 82 °C. the nitrogen purge assembly was replaced with an addition funnel. Ethanolamine (61.15 grams, 1.001 moles) was added drop wise from the addition funnel to the reactor contents over a period of 33 minutes. The resulting exotherm increased the temperature of the contents to 149 °C. The nitrogen purge assembly was re-attached.
  • Example 3 Diglycidyl ether of neopentyl glycol (200.0 grams, 216.28 g/mole, 0.9247 moles) and 2-methoxyethyl ether (92.6 grams) were weighed into a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 97 °C and the nitrogen purge assembly was replaced with an addition funnel. Ethanolamine (42.6 grams, 61.08 g/mole, 0.6974 mole) and 2-methoxyethyl ether (56.8 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 4 The product from Example 3 (5.11 grams) was dissolved in methanol (5.04 grams) and isopropanol (0.65 grams).
  • Example 5 Diglycidyl ether of neopentyl glycol (216.29 grams, 1.000 mole) and di(propylene glycol) methyl ether (76.80 grams) were weighed into a 1-liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 76 °C. The nitrogen purge system was replaced with an additional funnel.
  • 3-(Dimethylamino)propylamine (15.34 grams, 102.18 g/mole, 0.1502 mole), ethanolamine (51.92 grams, 0.8500 mole) and di(propylene glycol)methyl ether (65.50 grams) were weighed into a beaker and transferred to the addition funnel.
  • the solution of 3-(dimethylamino)propylamine and ethanolamine in di(propylene glycol)methyl ether was added dropwise over a period of 29 minutes.
  • the resulting exotherm increased the temperature of the contents to 183 °C.
  • the reactor contents started to climb the stirring rod. Only 77 % of the 3-(dimethylamino)propylamine and ethanol amine in di(propylene glycol) methyl ether solution was reacted before gellation.
  • Example 6 Diglycidyl ether of neopentyl glycol (200.14 grams, 0.9254 moles) and di(propylene glycol) methyl ether (92.54 grams) were weighed into a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 87 °C. The nitrogen purge system was replaced with an additional funnel. 3-(Dimethylamino) propylamine (1.43 grams, 0.01399 moles), ethanolamine (41.83 grams, 0.6848 moles) and di(propylene glycol)methyl ether (56.66 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 7 The product from Example 6 (9.94 grams) was dissolved in methanol (9.50 grams) and isopropanol (1.20 grams).
  • Example 8 Diglycidyl ether of neopentyl glycol (200.2 grams, 0.9256 moles) and di ⁇ ropylene glycol) methyl ether (70.11 grams) were weighed into a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 79 °C. The nitrogen purge system was replaced with an additional funnel. 3-(Dimethylamino) propylamine (2.87 grams, 0.0281 moles), ethanolamine (41.05 grams, 0.6721 moles) and di ⁇ ropylene glycol)methyl ether (60.13 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 9 The material from Example 8 (10.11 grams), methanol (9.70 grams) and isopropanol (1.24 grams) were blended together.
  • Example 10 Material from Example 8 (131.04 grams) and 93% sulfuric acid (9.33 grams) were weighed into a 4-neck 500-milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. Water (99.77 grams) was added. The contents were heated to 80 °C. and then cooled to room temperature.
  • Example 11 The material from Example 10 (13.59 grams), methanol (12.94 grams) and isopropanol (1.58 grams) were blended together.
  • Example 12 Diglycidyl ether of neopentyl glycol (200.06 grams, 0.9250 moles) and di ⁇ ropylene glycol) methyl ether (70.05 grams) were weighed into a 4-neck 500 milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 47 °C. The nitrogen purge system was replaced with an additional funnel. 3-(Dimethylamino) propylamine (3.93 grams, 0.03846 moles), ethanolamine (39.41 grams, 0.6452 moles) and di ⁇ ropylene glycol)methyl ether (60.12 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 13 The material from Example 12 10.10 grams), methanol (9.72 grams) and isopropanol (1.41 grams) were blended together to prepare a solution.
  • Example 14 1,2,7,8-Diepoxyoctane (58.27 grams, 140.18 g/mole, 0.4157 moles) and di ⁇ ropylene glycol) methyl ether (40.25 grams) were weighed into a 4-neck 250 milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 70 °C. The nitrogen purge system was replaced with an additional funnel.
  • Example 16 N, N, N'-trimethylethylenediamine (4.06 grams, 102.18 g/mole, 0.03973 moles) in di(propyleneglycol)methyl ether (20.08 grams) was added to all the material from Example 14 The contents were heated between 130 °C and 151 °C for 14 minutes and then cooled to room temperature.
  • Example 17 The material from Example 16 (8.02 grams), methanol (7.72 grams) and isopropanol (1.03 grams) were blended together while heating.
  • Example 18 Diglycidyl ether of neopentyl glycol (200.29 grams,0.9261 moles) and di ⁇ ropylene glycol) methyl ether (70.46 grams) were weighed into a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 78 °C. The nitrogen purge system was replaced with an additional funnel. 3-(Dimethylamino) propylamine (1.442 grams, 0.01411 moles), ethanolamine (41.89 grams, 0.4100 moles) and di ⁇ ropylene glycol)methyl ether (60.11 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 19 The material from Example 18 (7.65 grams), methanol (7.31 grams) and isopropanol (0.89 grams) was blended together.
  • Example 20 Diglycidyl ether of neopentyl glycol (200.29 grams, 0.9261 moles) and 2-(2- aminoethoxy)ethanol (73.42 grams, 105.14 g/mole, 0.6983 moles) were weighed into a 1- liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 66 °C. Within 3 minutes the reactants exothermed to 238 °C. The contents were cooled to 153 °C immediately. The reactor contents were a clear but red brown liquid. The contents were heated between 153 ° and 196 °C for 2 hours and 29 minutes. They were cooled to room temperature and had a viscosity of 369,000 at 25 °C.
  • Example 21 The material from Example 20 (12.96 grams) was dissolved in isopropanol (1.65 grams) and methanol (12.36 grams) with heat and shaking.
  • Example 22 Material from Example 20 (256.18 grams) and 2-(methoxyethyl) ether (109.79 grams) were heated to 112 °C in a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly to give a solution of 68.58 wt. % solids. The material dissolved in the 2-(methoxyethyl) ether when the temperature reached 72 °C. The reactor contents were cooled to room temperature and the viscosity at 26 °C was 898 cps.
  • Example 23 The material from Example 22 (9.31 grams), methanol (8.85 grams) and isopropanol (1.09 grams) were blended together.
  • Example 24 Diglycidyl ether of neopentyl glycol (100.06 grams, 0.4626 moles) and 2- methoxyethyl ether (55.33 grams) were weighed into a 1-liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 84 °C. The nitrogen purge system was replaced with an additional funnel. 2-(2-Aminoethoxy)ethanol (36.68 grams, 0.3489 moles) and 2- methoxyethyl ether (28.28 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 25 The material from Example 24 (8.06 grams) methanol (7.61 grams) and isopropanol (1.16 grams) were blended together.
  • Example 26 The material from Example 24 was heated in a 1 -liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly between 155 °C. and 160 °C for 4 hours and 45 minutes. The contents were cooled to room temperature. The viscosity was 201, 257 cps at 26 °C.
  • Example 27 The material from Example 25 (9.56 grams), methanol (9.04 grams) and isopropanol (1.06 grams) were blended together.
  • Example 28 Diglycidyl ether of neopentyl glycol (100.07 grams, 0.4627 moles) and heavy aromatic naptha (56.61 grams) were weighed into a 1-liter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 86 °C. The nitrogen purge system was replaced with an additional funnel. Additional, a portion of heavy aromatic naptha (28.06 grams) was added to the reactor contents. 2-(2-Aminoethoxy)ethanol (36.72 grams, 0.3492 moles) was weighed into a beaker and transferred to the addition funnel.
  • 2-(2- Aminoethoxy)ethanol was added dropwise resulting in an exotherm which quickly brought the reactor contents temperature to 182 °C.
  • the reactor contents were cooled to 156 °C and then the remaining 2-(2-aminoethoxy)ethanol was added.
  • the total addition time for 2-(2- aminoethoxy)ethanol was 18 minutes.
  • the nitrogen purge assembly was re-attached.
  • the contents were heated between 138 ° and 179 °C for 53 hours and 20 minutes.
  • the reactor contents were cooled to 105 °C and N-methyl-D-glucamine (6.82 grams, 0.03493 moles) was added.
  • the contents were heated between 142 °C and 186 °C for 2 hours and 43 minutes.
  • the final product had a viscosity of 100,857 cps at 25 °C.
  • Example 29 The mixed material from Example 28 (15.62 grams), methanol (14.89 grams) and isopropanol (1.84 grams) were blended together.
  • Example 30 Diglycidyl ether of neopentyl glycol (118.61 grams, 0.5484 moles) and 2- methoxyethyl ether (118.61 grams) were weighed into a 1-resin kettle equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 87 °C and the nitrogen purge assembly was replaced with an addition funnel.
  • Jeffamine XTJ-505 (209.49 grams, 0.3491 moles) and 2-methoxyethyl ether (52.78 grams) were weighed into a beaker and transferred to the addition funnel.
  • Example 31 The material from Example 30 (6.51 grams), methanol (6.24 grams) and isopropanol (0.79 grams) were blended together.
  • Example 32 Diglycidyl ether of neopentyl glycol (216.3 grams, 1.000 moles) and di ⁇ ropylene glycol)methyl ether (128.0 grams) were weighed into a 1-liter resin kettle equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The contents were heated to 83 °C and the nitrogen purge assembly was replaced with an addition funnel. Ethanolamine (61.05 grams, 0.9995 moles) and di ⁇ ropylene glycol) methyl ether (42.02 grams) were weighed into a beaker and transferred to the addition funnel. The solution of ethanolamine in di ⁇ ropylene glycol) methyl ether was added dropwise to the reactor contents over a period of 27 minutes.
  • the resulting exotherm increased the temperature of the contents to 156 °C.
  • the nitrogen purge assembly was re-attached.
  • the contents were heated between 140 °C and 151 °C for an additional 9 hours and 31 minutes.
  • Diethanolamine (10.55 grams, 105.14 g/mole, 0.1003 moles) was added dropwise over a period of 21 minutes between 145 °C and 149 °C.
  • the additional funnel was rinsed with about a gram of di ⁇ ropylene glycol) methyl ether into the reactor contents.
  • the reactor contents were cooled to room temperature giving a liquid with a Brookfield viscosity of 19,700 cps.
  • Example 33 62.73 wt. % Diethanolamine capped ethanolamine/ diglycidyl ether of neopentyl glycol copolymer in di ⁇ ropylene glycol) methyl ether (111.05 grams) from Example 8 was dissolved in water (79.12 grams). 54 wt. % Epichlorohydrin terminated polyethylene glycol methyl ether (92.26 grams, 5082 g/mole, 0.009803 moles) in water was added and stirred to give a brown-orange opaque colored liquid with a pH of 7.99. The pH was adjusted to a pH of 8.41 with 3.6-wt. % solution of sodium hydroxide (28.67 grams). The contents were transferred to a 4-neck 500 ml.
  • Example 34 The material from Example 33 (7.83 grams), methanol (7.52 grams) and isopropanol (0.96 grams) was blended together.
  • Example 35 62.35 wt % Diethanolamine (DEA) capped 3-(dimethylamino) propylamine (DMAPA)/ ethanolamine (EA)/ diglycidyl ether of neopentyl glycol (DGE NPG) te ⁇ olymer in di (propylene glycol) methyl ether (111.38 grams) from Example 6., 54 wt. % epichlorohydrin terminated polyethyleneglycol methyl ether (91.86 grams, 5082 g/mole, 0.009761 moles) in water, and water (78.96 grams) were added to a beaker and stirred to give a yellow brown colored liquid with a pH of 7.63.
  • DEA Diethanolamine
  • DMAPA 3-(dimethylamino) propylamine
  • EA ethanolamine
  • DGE NPG diglycidyl ether of neopentyl glycol
  • the pH was adjusted to a pH of 8.45 with 3.6 wt. % solution of sodium hydroxide (12.49 grams).
  • the viscosity of the contents was 107 cps.
  • the contents were transferred to a 4-neck 500 ml. round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly.
  • the reactor contents were heated between 80 ° and 91 °C for 4 hours and 20 minutes.
  • the viscosity was measured to be 285 cps and the pH was 7.62.
  • the pH was adjusted to a pH of 8.43 with 3.6 wt. % solution of sodium hydroxide (12.68 grams).
  • the viscosity was 245 cps.
  • Mw, Mn and polydispersity were determined to be 12658, 2537 and 5.0, respectively, by gel permeation chromatography.
  • the columns used in the GPC were TSK Gel G6000PW, G4000PW and G2000 PW (manufactured by Toya Soda Co ⁇ oration, Montgomeryville, PA 18936).
  • the eluent was 1:1 methanol to water with 1 wt % acetic acid and 0.1N sodium nitrate.
  • the flow rate and temperature were 0.8 ml/minute and 35 °C, respectively.
  • Example 36 The product from Example 35 (7.07 grams) was dissolved in methanol (6.79 grams) and isopropanol (0.84 grams).
  • Example 37 The material from Example 35 (10.04 grams), isopropanol (1.16 grams) and methanol (9.57 grams) were blended together.
  • Example 38 The material from Example 35. (5.05 grams), isopropanol (0.0872 grams), a wetting agent consisting of a blend of oxyalkylated alcohols and phosphate esters (1.058 grams) and methanol (3.825 grams) were blended together.
  • Example 39 Linear dodecylbenzenesulfonic acid (0.27 grams) was added and blended with the material of Example 38.
  • Example 40 66.82 wt. % N,N,N'-Trimethyl -1,3-propanediamine (TMPDA) capped 3- (dimethylamino)propylamine (DMAPA)/ ethanolamine (EA)/ diglycidyl ether of neopentyl glycol (DGE NPG) te ⁇ olymer in di ⁇ ropylene glycol) methyl ether (131.04 grams) from Example 8, water (99.77 grams) and 93 % sulfuric acid (9.33 grams) were added to a 4- neck 500 milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly and heated to 80 °C while stirring.
  • TMPDA N,N,N'-Trimethyl -1,3-propanediamine
  • DMAPA dimethylamino)propylamine
  • EA ethanolamine
  • DGE NPG diglycidyl ether of neopentyl glycol
  • the polymer begin to wrap around the stirring rod so a kill solution of 93% sulfuric acid (2.33 grams) and sodium chloride (4.00 grams) in water (40.06 grams) was added at 90 °C.
  • the contents were heated between 88 and 90 °C for an additional 35 minutes and then cooled to room temperature.
  • the pH of the material was 6.34.
  • the contents were transferred to a beaker and additional 93 wt. % sulfuric acid was added dropwise with stirring until a pH of 2.51 was obtained.
  • the contents were further digested by transferring them back to a 4- neck 500 milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly and heating between 77 and 86 °C for 8 hours and 21 minutes.
  • Final pH was 3.53.
  • Final viscosity at 25 °C was 220 cps.
  • Example 41 The material from Example 40 (12.63 grams) was diluted in water (37.85 grams).
  • Example 42 Poly(ethylene glycol) diglycidyl ether (280.54 grams, 0.5333 mole) was weighed into a 500 milliliter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The poly(ethylene glycol) diglycidyl ether was heated to 89 °C. A blend of 3-(dimethylamino)propylamine (0.9951 grams, 0.0097 moles) and ethanolamine (28.37 grams, 0.4645 moles) was added dropwise. The resulting exotherm quickly brought the temperature to 187 °C. The solution was cooled down to about 138 °C with an ice bath.
  • the reactor contents were maintained at a temperature between 150 ° and 157 °C for 3 hours and 39 minutes and then cooled to room temperature.
  • the Brookfield viscosity was 130, 000 cps at 25 °C.
  • Di ⁇ ropylene glycol) methyl ether (189.82 grams) was added to the contents to give a 943 cps liquid.
  • the reactor contents were then heated between 152 ° and 170 °C for 60 hours and 40 minutes giving a viscous liquid with a viscosity of 2606 cps.
  • Ethanolamine (3.72 grams, 0.0609 moles) in di ⁇ ropylene glycol) methyl ether (3.15 grams) was added to the reactor contents.
  • the reactor contents were heated between 153 ° to 173 °C for 7 hours and 15 minutes, at which point the vortex created by the stirrer disappeared.
  • Diethanolamine (2.43 grams, 0.0231 moles) in di ⁇ ropylene glycol) methyl ether (4.89 grams) was added to the contents.
  • the reactor contents were immediately cooled to room temperature to give a solution with a Brookfield viscosity of 182,000 cps at 25 °C.
  • Example 43 61.5 wt. % Diethanolamine (DEA) capped 3-(dimethylamino)propylamine (DMAPA)/ ethanolamine (EA)/ poly(ethylene glycol) diglycidyl ether terpolymer in di ⁇ ropylene glycol) methyl ether (111.86 grams) from Example 42, water (278.76 grams) and 67.12 wt. % epichlorohydrin terminated polyethyleneglycol methyl ether (91.8 grams, 5082 g/mole, 0.01212 moles) in water were added to a 600 ml beaker with a stirring bar. pH was measured to be 7.26.
  • DEA Diethanolamine
  • DMAPA 3-(dimethylamino)propylamine
  • EA ethanolamine
  • poly(ethylene glycol) diglycidyl ether terpolymer in di ⁇ ropylene glycol) methyl ether 111.86 grams
  • water 278.76 grams
  • the pH was readjusted to 8.50 by the addition of 23.95 grams of an aqueous 3.6 wt. % caustic solution.
  • the Brookfield viscosity was 186 cps at 25 °C.
  • the contents were transferred to a 4-neck 500-milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly and heated between 87 ° to 91 °C for 118 minutes. The contents were cooled to room temperature. The viscosity was 336.8 cps. pH was 7.0.
  • the pH was re-adjusted to 8.71 with 15.80 grams of an aqueous solution of 3.6 wt. % caustic.
  • the reactor contents were heated between 88 ° and 92 °C for 2 hours and 55 minutes.
  • the contents were cooled to room temperature and the viscosity was determined to be 1140 cps.
  • Example 44 50 wt. % Ethylene glycol diglycidyl ether (196.08 grams, 0.5628 moles) was weighed into a 500 milliliter 4-neck round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly. The (ethylene glycol) diglycidyl ether was heated to 78 °C. A blend of 3-(dimethylamino) propylamine (0.7242 grams, 0.0071 moles) and ethanolamine (19.98 grams, 0.3271 moles) was added dropwise in two minutes. The resulting exotherm quickly brought the temperature to 180 °C. The solution was cooled immediately with an ice bath.
  • Di ⁇ ropylene glycol) methyl ether (132.07 grams) was added in a seven minute period. Reactor temperature was 93 °C. The reactor contents were heated and maintained at a temperature between 149 °C and 155 °C for 46 minutes. Diethanolamine (1.48 grams, 0.01408 moles) in di ⁇ ropylene glycol) methyl ether (11.05 grams) was added to the contents, followed by the addition of di ⁇ ropylene glycol) methyl ether (10.0 grams). The reactor contents were heated between 152 °C to 153 °C for 10 minutes and then cooled to room temperature. The Brookfield viscosity was 87 cps at 25 °C.
  • the reactor contents were heated between 151 ° and 171 °C for 7 hours and 28 minutes and then cooled to room temperature.
  • the Brookfield viscosity was 1695 cps.
  • Example 45 58.77 wt. % Diethanolamine (DEA) capped 3-(dimethylamino)propylamine (DMAPA)/ ethanolamine (EA)/ ethylene glycol diglycidyl ether te ⁇ olymer in di ⁇ ropylene glycol) methyl ether (111.58 grams) from Example 44, water (79.36 grams) and 67. 12 Wt. % epichlorohydrin terminated polyethyleneglycol methyl ether (91.84 grams, 5082 g/mole, 0.01212 moles) in water were added to a 600 ml beaker with a stirring bar. pH was measured to be 8.42. The Brookfield viscosity was 157 cps at 25 °C.
  • DEA Diethanolamine
  • DMAPA 3-(dimethylamino)propylamine
  • EA ethanolamine
  • the contents were transferred to a 4-neck 500-milliliter round bottom flask equipped with a thermocouple and heating device, condenser, stirrer and nitrogen purge assembly and heated between 91 ° to 93 °C for 65 minutes.
  • the Brookfield viscosity was 749 cps.
  • the reactor contents (8.61 grams) were dissolved in isopropanol (1.12 grams) and methanol (7.87 grams).
  • the demulsifiers were evaluated in crude oil from the Energy Strawberry Formation in West Texas. The crude was collected on 3/24/2000. An acid corrosion inhibitor (ACI) was formulated using a benzyl chloride quaternary compound. A comparative nonionic, alkylated, phenolic-type demulsifier, EC-9547, is also exemplified in the Tables. The results from the demulsifier evaluation are summarized in the following Table IV.
  • the demulsifiers were evaluated in Miniham OPG from Andrews Co. 8000', Fasselman in Midland, Texas. The crude was collected on 11/2000.
  • the acid corrosion inhibitor (ACI) was a formulation containing a benzyl chloride quaternary compound. The results from the demulsifier evaluation are summarized in Table VI.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un désémulsionneur polymérique, des procédés pour la production de ce désémulsionneur, ainsi que des procédés pour l'utilisation de ce désémulsionneur. Le désémulsionneur selon l'invention est le produit de réaction d'au moins un groupe aminé et, facultativement, d'un deuxième groupe aminé comprenant un groupe aminé tertiaire, avec un composé diépoxy ou diglycidyle et un autre composé aminé que l'on fait ensuite réagir avec des groupes époxy n'ayant pas réagi. On fait ensuite réagir cette composition polymérique avec des composés contenant un agent de N-alkylation afin de produire de nouveaux désémulsionneurs servant à désémulsionner des formations pétrolifères.
PCT/US2002/039869 2001-12-20 2002-12-13 Nouveaux desemulsionneurs, leur preparation et leur utilisation dans des formations petroliferes WO2003053536A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002360587A AU2002360587A1 (en) 2001-12-20 2002-12-13 Novel demulsifiers,their preparation and use in oil bearing formations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/034,661 2001-12-20
US10/034,661 US7504438B1 (en) 2001-12-20 2001-12-20 Demulsifiers, their preparation and use in oil bearing formations

Publications (1)

Publication Number Publication Date
WO2003053536A1 true WO2003053536A1 (fr) 2003-07-03

Family

ID=21877807

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/039869 WO2003053536A1 (fr) 2001-12-20 2002-12-13 Nouveaux desemulsionneurs, leur preparation et leur utilisation dans des formations petroliferes

Country Status (3)

Country Link
US (1) US7504438B1 (fr)
AU (1) AU2002360587A1 (fr)
WO (1) WO2003053536A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005035627A1 (fr) * 2003-09-12 2005-04-21 Dow Global Technologies Inc. Polyhydroxyaminoether hydrosoluble et son procede de preparation
US7417011B2 (en) 2003-09-12 2008-08-26 Nalco Company Method and composition for recovering hydrocarbon fluids from a subterranean reservoir
WO2012068099A1 (fr) 2010-11-17 2012-05-24 Dow Global Technologies Llc Procédé faisant intervenir un dérivé alcoxylé et aminé de bisphénol a en tant que démulsifiant

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9169430B2 (en) 2012-10-30 2015-10-27 Ecolab Usa Inc. Chemical treatment method and additive used to treat fines migration and flow through porous media
CN103288169B (zh) * 2013-04-02 2014-11-05 浙江杭化科技有限公司 一种乙烯装置碱洗塔废碱液处理用破乳剂
US10253609B2 (en) 2014-04-29 2019-04-09 Ecolab Usa Inc. Permeability of subterranean reservoirs using acid diversion
CN103920415B (zh) * 2014-04-30 2015-05-20 河北工业大学 一种双子型阳离子表面活性剂及其制备方法
CN104498011B (zh) * 2014-12-22 2017-04-26 西南石油大学 一种用于稠油的树枝型油溶性降粘剂
CN109709252B (zh) * 2018-12-29 2021-08-17 奎克化学（中国）有限公司 一种环氧聚合物的检测方法
CN113429955B (zh) * 2021-06-24 2022-03-11 中国矿业大学 一种负载型聚醚聚季铵盐反相破乳剂的制备及其在三元复合驱采出水处理中的应用
CN113717061B (zh) * 2021-08-26 2024-01-30 长江大学 一种y型结构破乳剂及其制备方法和应用
CN114773589B (zh) * 2022-05-06 2024-02-23 麦加芯彩新材料科技(上海)股份有限公司 一种低温破乳剂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819222A (en) * 1953-08-26 1958-01-07 Petrolite Corp Process for breaking petroleum emulsions employing certain oxyalkylation products derived in turn from reactive nitrogen-containing compounds and polyepoxides
US4396499A (en) * 1981-12-02 1983-08-02 Texaco Inc. Demulsification of bitumen emulsions using water soluble salts of polymers
US4448992A (en) * 1981-09-12 1984-05-15 Hoechst Aktiengesellschaft Addition products from triethanolamine condensation products and bisglycidyl ethers and their use
US5648409A (en) * 1994-12-29 1997-07-15 Henkel Corporation Aqueous self-dispersible epoxy resin based on epoxy-amine adducts containing aromatic polyepoxide

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2136928A (en) 1934-12-10 1938-11-15 Ig Farbenindustrie Ag Manufacture of amines of high molecular weight, which are rich in nitrogen
BE494250A (fr) 1949-03-02
BE513382A (fr) 1951-08-07
US2723241A (en) 1952-08-18 1955-11-08 Petrolite Corp Process for breaking petroleum emulsions
NL210722A (fr) 1955-09-20
US3317471A (en) 1959-03-12 1967-05-02 Dow Chemical Co Thermoplastic resinous reaction product of a diglycidyl ether and an amino compound
US3350325A (en) 1964-07-31 1967-10-31 Dow Chemical Co Water soluble polymer of diglycidyl ether and an alkanolamine
US3349053A (en) 1964-07-31 1967-10-24 Dow Chemical Co Crosslinked water soluble polymer of diglycidyl ether and an alkanolamine
US4032514A (en) 1971-08-18 1977-06-28 Petrolite Corporation Oxyalkylated cyclic phenol-aldehyde resins and uses therefor
US3738945A (en) 1972-02-04 1973-06-12 H Panzer Polyquaternary flocculants
US3900423A (en) 1973-03-28 1975-08-19 Grace W R & Co Process for breaking emulsions
US4162244A (en) 1978-08-25 1979-07-24 The Dow Chemical Company Coating compositions
US4460627A (en) 1978-09-28 1984-07-17 Halliburton Company Polymeric well treating method
US4532052A (en) 1978-09-28 1985-07-30 Halliburton Company Polymeric well treating method
US4260019A (en) 1979-06-04 1981-04-07 Magna Corporation Method of recovering petroleum from a subterranean reservoir incorporating resinous polyalkylene oxide adducts
US4382852A (en) 1981-12-02 1983-05-10 Texaco Canada Resources, Inc. Demulsification of bitumen emulsions using cationic polymers
US4404096A (en) 1981-12-02 1983-09-13 Texaco, Inc. Demulsification of bitumen emulsions using ionenes
DE3223691A1 (de) 1982-06-25 1983-12-29 Hoechst Ag, 6230 Frankfurt Modifizierte veretherte phenol-aldehyd-kondensationsprodukte und deren verwendung zum spalten von erdoelemulsionen
US4617132A (en) 1985-04-01 1986-10-14 Halliburton Company Method of altering the permeability of a hydrocarbon-containing subterranean formation
DE3942766A1 (de) * 1989-12-23 1991-06-27 Basf Lacke & Farben Verfahren zum beschichten elektrisch leitfaehiger substrate, waessriger lack, epoxid-aminaddukt und verwendung des epoxid-aminadduktes als reibharz zur herstellung von pigmentpasten
DE69129055T2 (de) 1990-10-03 1998-08-06 Dow Chemical Co Hydroxy-funktionalisierte Polyetheramine zur Verwendung als Sperrschicht bei sauerstoffempfindlichen Materialien
AU643324B2 (en) 1990-10-09 1993-11-11 Bp Chemicals Limited Phenolic resin alkoxylates
DE4342721A1 (de) * 1993-12-15 1995-06-22 Hoechst Ag Elastisches Epoxidharz-Härter-System
US5464924A (en) 1994-01-07 1995-11-07 The Dow Chemical Company Flexible poly(amino ethers) for barrier packaging
US5565506A (en) * 1994-03-01 1996-10-15 Henkel Corporation Self-dispersing curable epoxy resins, dispersions made therewith, and coating compositions made therefrom
US5681907A (en) * 1996-01-04 1997-10-28 Air Products And Chemicals, Inc. Fast cure amines for ambient and subambient cure of epoxy resins comprising methylamine adducts
US5591812A (en) * 1996-01-26 1997-01-07 Air Products And Chemicals, Inc. Reactive accelerators for amine cured epoxy resins
US5834078A (en) 1997-08-14 1998-11-10 The Dow Chemical Company Hydroxy-functionalized poly(amino ether) salts
US6569983B1 (en) 2001-12-20 2003-05-27 Ondeo Nalco Energy Services, L.P. Method and composition for recovering hydrocarbon fluids from a subterranean reservoir

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2819222A (en) * 1953-08-26 1958-01-07 Petrolite Corp Process for breaking petroleum emulsions employing certain oxyalkylation products derived in turn from reactive nitrogen-containing compounds and polyepoxides
US4448992A (en) * 1981-09-12 1984-05-15 Hoechst Aktiengesellschaft Addition products from triethanolamine condensation products and bisglycidyl ethers and their use
US4396499A (en) * 1981-12-02 1983-08-02 Texaco Inc. Demulsification of bitumen emulsions using water soluble salts of polymers
US5648409A (en) * 1994-12-29 1997-07-15 Henkel Corporation Aqueous self-dispersible epoxy resin based on epoxy-amine adducts containing aromatic polyepoxide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005035627A1 (fr) * 2003-09-12 2005-04-21 Dow Global Technologies Inc. Polyhydroxyaminoether hydrosoluble et son procede de preparation
US7417011B2 (en) 2003-09-12 2008-08-26 Nalco Company Method and composition for recovering hydrocarbon fluids from a subterranean reservoir
US7678872B2 (en) 2003-09-12 2010-03-16 Dow Global Technologies, Inc. Process for preparing water-soluble polyhydroxyaminoether
US7893136B2 (en) 2003-09-12 2011-02-22 Dow Global Technologies, Inc. Water soluble co-polyhydroxyaminoether and solution thereof
WO2012068099A1 (fr) 2010-11-17 2012-05-24 Dow Global Technologies Llc Procédé faisant intervenir un dérivé alcoxylé et aminé de bisphénol a en tant que démulsifiant

Also Published As

Publication number Publication date
US7504438B1 (en) 2009-03-17
AU2002360587A1 (en) 2003-07-09

Similar Documents

Publication Publication Date Title
US6569983B1 (en) Method and composition for recovering hydrocarbon fluids from a subterranean reservoir
US7504438B1 (en) Demulsifiers, their preparation and use in oil bearing formations
US7893136B2 (en) Water soluble co-polyhydroxyaminoether and solution thereof
KR100193921B1 (ko) 자체 유화성 에폭시 경화제
US4558120A (en) Dense star polymer
EP2199338B1 (fr) Polyétheralkanolamines en forme de peigne dans des encres
EP2209836B1 (fr) Polyalcanolamines alcoxylés
WO2005028589A1 (fr) Procede et composition destines a recuperer des hydrocarbures fluides d'un reservoir souterrain
US5401439A (en) Oil-demulsifiers based on an alkoxylate and preparation of this alkoxylate
WO1984002705A1 (fr) Polymeres denses en etoile et procede de production de polymeres denses en etoile
US4448708A (en) Use of quaternized polyamidoamines as demulsifiers
US4546151A (en) Oxyalkylated polyamidoamines and their preparation
US5053496A (en) Low viscosity statistical monofunctional carboxylic-terminated, amine-terminated, or epoxy-terminated reactive liquid rubber polymers, and a process for preparation thereof
CA2057758A1 (fr) Compositions a base de resine d'epoxyde emulsifiables dans l'eau
CA1336843C (fr) Produits d'addition d'ether glycidylique esterifie et leur utilisation
US5241016A (en) Epoxy adhesives containing aminated, long chain monoepoxide capped polyols
US4457860A (en) Use of heterocyclic ammonium polyamidoamines as demulsifiers
JPH01153721A (ja) 分枝状の第四ポリオキシアルキレン−コポリエステルそして用途
US11261282B2 (en) PEO-PPO-PEO triblock bipolymers, with amphoteric endings, as demulsifying agents for heavy crude oils
US5191033A (en) Epoxy resin composition containing aminated epoxy resin-alkylene oxide polyols
JPH03229771A (ja) 水性顔料ペーストの製造法およびそれによって製造された顔料ペースト
US5723565A (en) Epoxy curing agents
WO2000047524A1 (fr) Procede de traitement des eaux usees

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP